KR101721612B1 - Pet container and compositions having enhanced mechanical properties and gas barrier properties - Google Patents

Abstract

A container comprising a polyester composition having enhanced mechanical properties is provided. The polyester composition comprises a polyester and a creep modifier. In certain embodiments, the polyester ingredients include polyesters, crepe modifiers, and gas barrier additives. In certain embodiments, the crepe modifier is a molecule or polymer comprising dianhydride, bis-lactam, bis-oxazole, and epoxide.

Description

FIELD OF THE INVENTION [0001] The present invention relates to PET containers and compositions having enhanced mechanical properties and gas barrier properties,

The present invention relates to polyester products such as poly (ethylene terephthalate) containers. More particularly, the present invention relates to a polyester container for use in applications where enhanced mechanical properties are desired.

Polyethylene terephthalate and its copolyester (hereinafter collectively referred to as "PET") are widely used for preparing containers for carbonated soft drinks, juices, water and the like due to their excellent combination of transparency, mechanical properties and gas barrier properties have. Despite these desirable features, the oxygen and carbon dioxide gas barrier properties of PET limit the application of PET to packaging oxygen sensitive products such as beer, juice and tea products, as well as smaller size packaging. There is a widely expressed need to further improve the gas barrier properties of PET in the packaging industry.

The relatively high permeability of PET to carbon dioxide limits the use of smaller PET containers for packaging carbonated soft drinks. The penetration rate of carbon dioxide through the PET container is in the range of 3 to 14 cc per day at room temperature, or 1.5 to 2% per main loss rate, depending on the size of the vessel. The smaller the vessel, the larger the ratio of surface area to volume, and the greater the relative loss rate. For this reason, PET containers are currently used only as larger containers for packaging carbonated soft drinks, and metal can and glass containers have been selected for smaller carbonated soft drink containers.

The amount of carbon dioxide remaining in the packaged carbonated soft drink determines its shelf life. Generally, the carbonated soft drink container is filled with approximately 4 volumes of carbon dioxide per volume of water. Generally, when 17.5% of the carbon dioxide in the container is lost due to the infiltration of carbon dioxide through the container side wall and the lid, the packaged carbonated soft drink is considered to have reached its shelf life limit. After the PET bottle is filled with approximately 4 volumes of carbon dioxide, the PET bottle will slowly expand over time due to the creep of the PET molecules under pressure. The level of carbonation is reduced due to bottle expansion. Accordingly, the penetration rate of the PET to the carbon dioxide and the degree of the bottle expansion due to the PET molecule creep determine the shelf life of the packaged carbonated beverage, and accordingly the suitability of the PET as the packaging material is determined.

While several techniques have been developed or developed to enhance the barrier properties of PET to small gas molecules, some techniques are too expensive and other techniques are not desirable for PET mechanical properties, stretch ratio, and / or transparency It can cause change. Efforts to improve the carbonation storage life of PET bottles by controlling the PET bottle creep have hardly been made.

There is therefore a need in the art to enhance the barrier properties of PET for use in packaging carbonated beverages and oxygen sensitive beverages and food products, for example, in applications requiring enhanced barrier properties, It is required that it does not substantially affect the stretching ratio of the PET and / or does not negatively affect the transparency of the PET.

SUMMARY OF THE INVENTION

The present invention addresses the above described needs by providing a polyester container with enhanced mechanical properties comprising a polyester composition comprising a polyester and a crepe modifier. According to another embodiment, there is provided a polyester composition comprising a polyester, a creep modifier and optional gas barrier additives.

In one aspect herein, the polyester composition comprises a crepe modifier of the formula (I): < EMI ID =

Wherein R ¹ , R ² , R ³ and R ⁴ may independently of each other be a heteroatom, S may be a carbon atom, or a C ₁ -C ₃ divalent or _trivalent hydrocarbon; Each heteroatom, or a carbon atom, or a C ₁ -C ₃ divalent or _trivalent hydrocarbon, may be unsubstituted or substituted with one or more C ₁ -C ₁₀ alkyl groups, which may be unsubstituted or substituted with one or more functional moieties, Hydrocarbyl,

i, ii, iii, iv, v and vi independently of one another include a single, double or triple bond; When i is a double bond, ii and vi are single bonds; When ii is a double bond, i and iii are single bonds; When iii is a double bond, ii and iv are single bonds; When iv is a double bond, iii and v are single bonds; When v is a double bond, iv and vi are single bonds; When vi is a double bond, i and v are single bonds; vii may not be a single bond, a double bond, or R ³ and R ⁴ at all;

m, n, o, and p independently of one another can be 0 or 1; when m is 0, bonds ii and iii form a single continuous bond; when n is 0, the bonds vi and v form a single continuous bond; when o is 0, R < ⁴ > is bonded to R < ¹ > When p is 0, R < ³ > is bonded to R < ² > by a single bond.

In another embodiment of the present invention, the polyester composition comprises a creping agent having the formula (II): < EMI ID =

In the above formulas, A, A ', A ", E, D, G, G', G", L and J each independently represent a hetero atom, S is a carbon atom or a C ₁ -C ₃ divalent or _trivalent hydrocarbon You can; Each heteroatom, a carbon atom or a C ₁ -C ₃ divalent or _trivalent hydrocarbon, is optionally substituted with one or more C ₁ -C ₁₀ hydrocarbons, which may be unsubstituted or substituted with one or more functional moieties, Carbamoyl;

i, ii, iii, iv, v, vi, vii, viii, ix, and x may independently of each other include a single or double bond; When i is a double bond, ii and v are single bonds; When ii is a double bond, i and iii are single bonds; When iii is a double bond, ii and iv are single bonds; When iv is a double bond, iii and v are single bonds; When v is a double bond, i and iv are single bonds; When vi is a double bond, vii and x are single bonds; When vii is a double bond, vi and viii are single bonds; When viii is a double bond, vii and ix are single bonds; When ix is a double bond, viii and x are single bonds; When x is a double bond, vi and ix are single bonds;

b, c, d, e, f, g, h, i, j and k may be independently 0 or 1;

a may be 0 or 1;

R < ⁵ > is a heteroatom or a group which may be unsubstituted or substituted with one or more C ₁ -C ₁₀ hydrocarbyl which may be unsubstituted or substituted with one or more functional moieties, one or more heteroatoms, C ₁ -C ₁₀ divalent hydrocarbons.

In another aspect of the present invention, the polyester composition comprises a crepe modifier having a chemical structure of the formula (III): < EMI ID =

Wherein R ⁶ and R ⁷ are, independently of each other, phenyl which is unsubstituted or substituted by one or more C ₁ -C ₁₀ hydrocarbyl, which may be substituted by one or more functional moieties, one or more heteroatoms, ₅ teeth which may be substituted by C ₁ -C may comprise a hydrocarbon.

In another embodiment of the present invention, the polyester composition comprises a crepe modifier having a chemical structure of the formula (IV): < EMI ID =

Wherein A ¹ , A ² , R ⁸ , R ⁹ and R ¹⁰ are independently of each other a heteroatom, a sagas hydrocarbon, a C ₁ -C ₁₀ divalent or trivalent hydrocarbon, or an unsubstituted or substituted at least one functional moiety It can may include a C ₁ -C ₁₀ hydrocarbyl, which can be;

Each heteroatom, or a carbon atom, or a C ₁ -C ₁₀ divalent or trivalent hydrocarbon, is optionally substituted with one or more C ₁ -C ₁₀ hydrocarbons, which can be unsubstituted or substituted with one or more functional moieties or one or more functional moieties, Carbamoyl;

m ', n', and p 'may be, independently of each other, 0 or 1;

i, ii, and iii may be, independently of each other, a single bond or a double bond;

t, u, v, and w may be, independently of each other, a single bond, a double bond, or a triple bond;

q, r, and s may be from 0 to 10,000.

In another embodiment of the present invention, the polyester composition preferably comprises a crepe modifier of the formula (V): < EMI ID =

Wherein R may comprise a heteroatom, or a C ₁ -C ₁₀ hydrocarbyl which may be unsubstituted or substituted with one or more functional moieties;

m ", n ", and o ", independently of one another, may be from 0 to 1,000.

In another embodiment of the present invention, the polyester composition comprises a crepe modifier of the formula (VI)

Wherein R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ , independently of each other, may comprise a heteroatom, S is a carbon atom or a C ₁ -C ₃ divalent or _trivalent hydrocarbon; Each heteroatom, a carbon atom or a C ₁ -C ₃ divalent or _trivalent hydrocarbon, is optionally substituted with one or more C ₁ -C ₁₀ hydrocarbons, which may be unsubstituted or substituted with one or more functional moieties, ≪ / RTI >

i, ii, iii, iv, v, vi, vii, viii, ix, x, and xi are independently of each other a single bond or a double bond; When i is a double bond, ii and vi are single bonds; When ii is a double bond, i, iii, and vii are single bonds; When iii is a double bond, ii, iv, vii, and xi are single bonds; When iv is a double bond, iii, v, and xi are single bonds; When v is a double bond, vi and iv are single bonds; When vi is a double bond, i and v are single bonds; When vii is a double bond, ii, iii, and viii are single bonds; When viii is a double bond, vi and ix are a single bond; When ix is a double bond, viii and x are single bonds; When x is a double bond, ix and xi are single bonds; When xi is a double bond, iv, x, and iii are single bonds.

In another embodiment of the present invention, the polyester composition comprises a crepe modifier of formula (VII): < EMI ID =

Wherein R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² independently of one another are a heteroatom, S is a carbon atom or a C ₁ -C ₃ divalent or _trivalent hydrocarbon You can; Each heteroatom, a carbon atom, or a C ₁ -C ₃ divalent or _trivalent hydrocarbon, is optionally substituted with one or more C ₁ -C ₁₀ hydrocarbons, which can be unsubstituted or substituted with one or more functional moieties, Carbamoyl;

xi, xi, xi, xi, xi, xi, xi, xi, xi, vii, vii, viii, xi, xi, xii, xiii, xiv, xv, xvi, Or a single bond; When i is a double bond, ii and vi are single bonds; When ii is a double bond, i, iii, and vii are single bonds; When iii is a double bond, ii, iv, vii, and xi are single bonds; when iv is a double bond, iii, v, xi, and xii are single bonds; When v is a double bond, vi, iv, and xii are single bonds; When vi is a double bond, i and v are single bonds; When vii is a double bond, ii, iii and viii are single bonds; When viii is a double bond, vii and ix are a single bond; When ix is a double bond, viii and x are single bonds; When x is a double bond, ix, xi, and xiii are single bonds; When xi is a double bond, iii, iv, xiii and x are single bonds; When xii is a double bond, v, iv, xvi, and xiv are single bonds; When xiv is a double bond, xii, xvi, xv, and xix are single bonds; When xv is a double bond, xiii, xvii, xiv, and xix are single bonds; When xiii is a double bond, xi, x, xv, and xvii are single bonds; When xvi is a double bond, xii, xiv, and xviii are single bonds; When xviii is a double bond, xvi and xxi are single bonds; When xxi is a double bond, xviii and xxii are single bonds; When xxii is a double bond, xxi, xix, and xxiii are single bonds; When xix is a double bond, xiv, xv, xxii, and xxiii are only a single bond; When xxiii is a double bond, xix, xxii, and xxiv are single bonds; When xxiv is a double bond, xxiii and xx are single bonds; When xx is a double bond, xvii and xxiv are a single bond; When xvii is a double bond, xv, xiii and xx are single bonds.

According to another embodiment, a method is provided for enhancing the mechanical properties of a polyester container, including forming a polyester composition by blending the polyester with a crepe modifier (s). According to certain embodiments, the polyester composition may be formed of an article, such as a container.

In yet another embodiment, the step of forming the container includes stretch blow molding. Certain embodiments provide a polyester container, e. G., A PET container, having enhanced mechanical properties. Other specific embodiments provide polyester containers having both enhanced mechanical properties and enhanced gas barrier properties, especially gas barrier properties enhanced for carbon dioxide and oxygen. This is particularly suitable for packaging carbonated soft beverages and oxygen sensitive beverages and foods according to certain embodiments of the present invention. Certain embodiments can achieve such enhanced gas barrier properties while maintaining acceptable physical properties and transparency.

Other objects, features and advantages of the present invention will become apparent from the following detailed description, drawings, and claims.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram of a system for manufacturing PET containers with enhanced gas barrier properties according to one embodiment of the present invention.
Figure 2 is a mouth cross-sectional view of a molded container preform made according to one embodiment of the present invention.
Figure 3 is a mouth cross-sectional view of a blow molded container made from the preform of Figure 2 according to one embodiment of the present invention.
4 is a perspective view of a packaged beverage made according to one embodiment of the present invention.
Figure 5 is a graph illustrating the average creep rate for a container made according to one embodiment of the present invention.

A polyester container with enhanced mechanical properties and a method of making a polyester container with enhanced mechanical properties are provided herein. A polyester container according to embodiments of the present application and a method of manufacturing such a container are further described below with reference to Figures 1-5.

I. Polyester composition

The embodiments provided herein may be applied to any polyester and may be suitable for use in applications where enhanced mechanical properties are desired. Non-limiting examples of polyesters suitable for use in the embodiments provided herein may include PET copolymers, polyethylene naphthalate (PEN), polyethylene isophthalate, and the like. PET copolymers are particularly useful because they are used for many barrier applications such as films and containers. Suitable containers include, but are not limited to, bottles, drums, carafe, cooler, and the like.

Polyesters containing PET copolymers have free spaces between polymer chains. As is known to those skilled in the art, the amount of free space in the polyester, such as PET copolymers, determines its barrier properties to gas molecules. The smaller the free space, the less the gas diffusion and the better the barrier to gas molecules. In general, it has been found that placing a gas barrier additive in the free space improves the gas barrier properties of the polyester composition. The Applicant has found that the crepe control agent provided herein can also enhance the gas barrier properties of the polyester while enhancing the mechanical properties of the polyester.

In one particular embodiment, the polyester composition comprises a polyester, and a creep conditioner as further described below. The crepe modifier of the polyester composition has a low loading level, desirably from about 200 to about 2000 ppm of the polyester composition, more desirably from about 500 to about 1000 ppm of the polyester composition, Enhances the gas barrier properties of the polyester composition in the range of from about 750 to about 1000 ppm of the polyester composition. The loading level of the crepe modifier should be maintained at a level sufficient to provide enhanced mechanical and gas barrier properties without substantially impairing this characteristic or visual appearance of the polyester composition. For example, those skilled in the art will recognize that turbidity or color change containers for packaged beverages are generally undesirable.

In certain embodiments, the polyester compositions provided herein may further comprise suitable gas barrier enhancing additives. Although suitable gas barrier toughening additives are known to those skilled in the art, the Applicant has found that the combination of the crepe modifier and gas barrier toughening additive provided herein additionally enhances the gas barrier properties of the polyester composition. Such gas barrier enhancing additives are described further below in co-pending U. S. Patent Application No. 12 / 629,379, U.S. Patent Application Publication No. 2005/0221036, U.S. Patent Application Publication 2006 / 0275568, and U.S. Patent Application Publication 2007/0082156.

Suitable PET copolymers for use in embodiments of the present invention may include a diol component having repeating units from ethylene glycol and a diacid component having repeating units from terephthalic acid. In certain embodiments, the PET copolymer has less than 20% diacid modification, less than 10% glycol modification, or both, based on 100 mole% of the diacid component and 100 mole% of the diol component. Such PET copolymers are well known.

The polyester may be prepared using any suitable polycondensation catalyst; Applicants have previously discovered that certain polycondensation catalysts may be particularly suitable for use with gas barrier toughening additives. Such polycondensation catalysts are described in U.S. Patent Publication No. 2006/0275568. In one embodiment, the polyester may be made using at least one first polycondensation catalyst selected from the group consisting of metals of Groups 3, 4, 13, and 14 of the Periodic Table. The polyester composition may comprise the remainder of the catalyst remaining in the polyester from the formation of the polyester, and the remainder of the catalyst may comprise at least part of the first polycondensation catalyst. In some embodiments, the remainder of the catalyst may be present in the polyester composition in an amount up to 250 ppm, preferably below that.

Gas barrier toughening additives and polyesters can cause ester exchange reactions, which can lead to problems in the application of the container, for example, lowering the IV of the polyester composition to unacceptable levels. It is believed that the transesterification reaction in the PET copolymer resin is catalyzed by the residual polycondensation catalyst. Thus, in one embodiment, the residual polycondensation catalyst in the polyester can be deactivated. One way to deactivate such a catalyst is to add a catalyst deactivating compound, such as a phosphorus containing compound, to the polyester composition. After the catalyst is deactivated, these will not catalyze the transesterification reaction and this reaction will be slowed during the melt processing of the polyester, for example the PET copolymer, and the gas barrier toughener additive blend. The phosphorus-containing compound includes both organic compounds and inorganic compounds. Examples include, but are not limited to, phosphoric acid, polyphosphoric acid, and tris (2,4-di-t-butylphenyl) phosphite, trismonononyl phenyl phosphite.

The polycondensation catalyst deactivation agent is optionally added to the polyester composition in an amount sufficient to deactivate the polycondensation catalyst residue in the polyester composition so that the gas barrier toughening additive can sufficiently enhance the gas barrier properties of the polyester composition and the resulting polyester container Can be added. For example, such additives may be added to the polyester composition in an amount less than 2000 ppm. According to one embodiment, the polycondensation catalyst deactivator may be present in the polyester composition in an amount of from about 10 to about 500 ppm by weight of the polyester composition or from about 100 to about 500 ppm by weight of the polyester composition.

Despite the addition of polycondensation deactivators, the range of inactivation of the polycondensation is not clear, and when the particular polycondensation catalyst is used in the formation of the polyester by polycondensation reaction, the decomposition of the polyester May not be sufficient to ignore. Thus, in another embodiment, the polyester composition may comprise a second polycondensation catalyst selected from the group consisting of cobalt, antimony, zinc, manganese, magnesium, cesium, calcium and cadmium. Those skilled in the art will recognize that the amount of the second polycondensation catalyst present in the polyester composition should be maintained below a level that can significantly lower the I.V. of the polyester composition below an acceptable level. Thus, in one embodiment, the second polycondensation catalyst may be present in the polyester composition in an amount of less than or equal to 3 ppm of the polyester composition. In detail, the reactivity of conventional polycondensation catalysts such as cobalt, antimony, zinc, manganese, magnesium, cesium, calcium, and cadmium is determined by the reaction of cobalt, antimony, zinc, manganese, magnesium, cesium, calcium, Is not relieved to the extent necessary to use phosphorus-based deactivators as a viable alternative to the substantial reduction or elimination of the contained metal catalyst residues.

The reaction between the gas barrier toughening additive and the polyester composition can reduce I.V. of the polyester composition and the resulting vessel preform. PET with a significantly lower I.V. can not be used in blow molded containers, such as beverage containers, because the I.V. is low. PET produces containers with poor mechanical performance, such as creep, drop impact resistance, and the like. Also, low I.V. PET containers made from PET generally have poor stress cracking resistance resistance for carbonated soft drink applications, which is undesirable in container applications. In order to prepare container preforms and containers with suitable physical properties and IV suitable for effective molding of preforms and blow molding of such preforms into containers, the polyester composition preferably has a porosity of at least 0.65, more preferably about 0.65 To about 1.0, and even more preferably from about 0.70 to about 0.86. All units for IV herein are dL / g measured in accordance with ASTM D4603-96, wherein the IV of the PET-based resin is 60/40 (by weight) phenol / 1,1,2,2-tetrachloroethane solution ≪ / RTI > by weight.

As discussed above, polyesters having a residual catalyst with minimal or no cobalt, antimony, zinc, manganese, magnesium, cesium, calcium and cadmium substantially alleviate the reduction in I.V. The total content of cobalt, antimony, zinc, manganese, magnesium, cesium, calcium and cadmium is preferably less than 3 ppm. According to a particular embodiment, suitable gas barrier toughening additives for PET polymers and copolymers are titanium and aluminum-based metals in the absence of the balance containing cobalt, antimony, zinc, manganese, magnesium, cesium, calcium or cadmium. Is blended with a polyester having a catalyst. The periodicity of the elements in the modern periodic table suggests that similar chemical reactivity exists in one group. As such, zirconium and hafnium may be useful as analogues to titanium catalysts, and gallium, indium and thallium may be useful analogs of aluminum. Germanium, tin, and lead from group 14 may be suitable.

III . Creep conditioner Creep Control Agent )

In one aspect of the present invention, the polyester composition comprises a crepe modifier of the formula (I)

Wherein R ¹ , R ² , R ³ and R ⁴ may independently of each other be a heteroatom, S may be a carbon atom, or a C ₁ -C ₃ divalent or _trivalent hydrocarbon; Each heteroatom, or a carbon atom, or a C ₁ -C ₃ divalent or _trivalent hydrocarbon, may be unsubstituted or substituted with one or more C ₁ -C ₁₀ alkyl groups, which may be unsubstituted or substituted with one or more functional moieties, Hydrocarbyl,

i, ii, iii, iv, v and vi independently of one another include a single, double or triple bond; When i is a double bond, ii and vi are single bonds; When ii is a double bond, i and iii are single bonds; When iii is a double bond, ii and iv are single bonds; When iv is a double bond, iii and v are single bonds; When v is a double bond, iv and vi are single bonds; When vi is a double bond, i and v are single bonds; vii may not be a single bond, a double bond, or R ³ and R ⁴ at all;

m, n, o, and p independently of one another can be 0 or 1; when m is 0, bonds ii and iii form a single continuous bond; when n is 0, the bonds vi and v form a single continuous bond; when o is 0, R < ⁴ > is bonded to R < ¹ > When p is 0, R < ³ > is bonded to R < ² > by a single bond.

In certain embodiments of the compounds of formula (I) wherein m, n, o, and p are 0 and i, ii / iii, iv, and v / vi are single bonds, the creep conditioner is a compound of formula: -1,2,3,4-tetracarboxylic acid dianhydride:

In another embodiment of the compounds of formula (I) wherein n, o, and p are 0 and m is 1 and i, ii, iii, iv, and v / vi are single bonds and R ¹ is oxygen, 2,3,4,5-tetrahydro-2,3,4,5-tetracarboxyl-furan dianhydride, which is a compound of the formula:

m and n are 1, o and p are 0, R ¹ and R ² are trivalent hydrocarbons containing 1 carbon atom, i, iii, and v are double bonds and ii, iv and vi are single bonds. In another embodiment of the compounds of I), the crepe modifier comprises a pyromellitic dianhydride which is a compound of the formula:

i, ii, iii, iv, v, and vi are single bonds, wherein m, n, o, and p are 1 and R ¹ , R ² , R ³ , and R ⁴ are ^trivalent hydrocarbons containing one carbon atom In another embodiment of the compounds of formula (I) wherein vii is a double bond, the creep conditioner is a compound of the formula: bicyclo [2.2.2] oct-3,4-en-1,2,5,6-tetra Carboxylic acid dianhydride: < RTI ID = 0.0 >

In another embodiment of the present invention, the polyester composition comprises a creping agent having the formula (II): < EMI ID =

In the above formulas, A, A ', A ", E, D, G, G', G", L and J each independently represent a hetero atom, S is a carbon atom or a C ₁ -C ₃ divalent or _trivalent hydrocarbon You can; Each heteroatom, a carbon atom or a C ₁ -C ₃ divalent or _trivalent hydrocarbon, is optionally substituted with one or more C ₁ -C ₁₀ hydrocarbons, which may be unsubstituted or substituted with one or more functional moieties, Carbamoyl;

i, ii, iii, iv, v, vi, vii, viii, ix, and x may independently of each other include a single or double bond; When i is a double bond, ii and v are single bonds; When ii is a double bond, i and iii are single bonds; When iii is a double bond, ii and iv are single bonds; When iv is a double bond, iii and v are single bonds; When v is a double bond, i and iv are single bonds; When vi is a double bond, vii and x are single bonds; When vii is a double bond, vi and viii are single bonds; When viii is a double bond, vii and ix are single bonds; When ix is a double bond, viii and x are single bonds; When x is a double bond, vi and ix are single bonds;

b, c, d, e, f, g, h, i, j and k may be independently 0 or 1;

a may be 0 or 1;

R < ⁵ > is a heteroatom or a group which may be unsubstituted or substituted with one or more C ₁ -C ₁₀ hydrocarbyl which may be unsubstituted or substituted with one or more functional moieties, one or more heteroatoms, C ₁ -C ₁₀ divalent hydrocarbons.

D, J, G ', b, c, d, e, f, g, h, i, j and k are 1, a is 0, E and L are bivalent hydrocarbons containing 1 carbon atom, Iv, v, vi, viii, ix, and x are single bonds, and iii and vii are double bonds, wherein A and G " Linkage and the ring comprising A, A ', A ", D and E is linked to the ring comprising G, G', G", L, and J by a single bond between D and J, ), The crepe modifier is 4 ' -bisoxazoline of the formula: < RTI ID = 0.0 >

and E and L, wherein a, b, c, d, e, f, g, h, i, j and k are 1, a is 0 and A ', D, J, G' I, iii, iv, v, vi, viii, ix, and x are each a single bond containing a single carbon atom, A and G are nitrogen, A "and G" are oxygen, ii and vii are double bonds, (II) wherein the ring containing A, A ', A ", D and E is bonded to the ring comprising G, G', G", L and J by a single bond between D and J, ), The creep conditioner is 4,4'-bisoxazoline of the formula:

b, c, d, e, f, g. wherein A, G and G 'are H, i, j, and k are 1, a is 0, A "and G" A ring containing A, A ', A ", D, and E is a divalent hydrocarbon containing an atom and v and x are double bonds and i, ii, iii, iv, vi, vii, viii, In another embodiment of the compound of formula (II) wherein R < 2 > is bonded to the ring comprising G, G ', G ", L, and J by a single bond between D and J, '- bis (2-oxazoline):

and R < ⁵ >, E and R < ³ > are each independently selected from the group consisting of a, b, c, d, e, f, g, h, L is a bivalent hydrocarbon comprising one carbon atom, A and G are nitrogen, A "and G" are oxygen, ii and vii are double bonds and i, iii, iv, v, vi, viii, In another embodiment of the compound of formula (II) wherein R is a single bond and R < ⁵ > is bonded to D and J, the creep conditioner is bis (4,5-

d, e, f, g, k, j, and a is 1 and b, c, h, and i is 0, and E and L are oxygen and R ^5, A ", and G" contains one carbon atom V, ix, and x are single bonds, E and A "are bonded together directly by a single bond, and L and G" are bonded to each other by a single bond, if D and J are trivalent hydrocarbons, (II) wherein R < ⁵ > is bonded to D and J, the crepe modifier is bis (4,5-dihydrooxazol-5-yl)

In another aspect of the present invention, the polyester composition comprises a crepe modifier having a chemical structure of the formula (III): < EMI ID =

Wherein R ⁶ and R ⁷ are, independently of each other, phenyl which is unsubstituted or substituted by one or more C ₁ -C ₁₀ hydrocarbyl, which may be substituted by one or more functional moieties, one or more heteroatoms, ₅ teeth which may be substituted by C ₁ -C may comprise a hydrocarbon.

In one particular embodiment of the compound of formula (III), wherein R < ⁶ > and R < ⁷ > are bivalent hydrocarbons comprising 5 carbon atoms, the crepe modifier is bis- caprolactam carbonyl of the formula:

In another embodiment of the present invention, the polyester composition comprises a crepe modifier having a chemical structure of the formula (IV): < EMI ID =

Wherein A ¹ , A ² , R ⁸ , R ⁹ and R ¹⁰ are independently of each other a heteroatom, a sagas hydrocarbon, a C ₁ -C ₁₀ divalent or trivalent hydrocarbon, or an unsubstituted or substituted at least one functional moiety It can may include a C ₁ -C ₁₀ hydrocarbyl, which can be;

Each heteroatom, or a carbon atom, or a C ₁ -C ₁₀ divalent or trivalent hydrocarbon, is optionally substituted with one or more C ₁ -C ₁₀ hydrocarbons, which can be unsubstituted or substituted with one or more functional moieties or one or more functional moieties, Carbamoyl;

m ', n', and p 'may be, independently of each other, 0 or 1;

i, ii, and iii may be, independently of each other, a single bond or a double bond;

t, u, v, and w may be, independently of each other, a single bond, a double bond, or a triple bond;

q, r, and s may be from 0 to 10,000.

(IV) wherein q, r, p 'm' is 0 and s and n 'are 1 and R ⁸ is isobenzofuran-1,3-dione and i, ii and iii are double bonds. In certain embodiments, the crepe modifier is a biphenyl-2,3,2'3'-tetracarboxylic acid dianhydride having the formula:

q, and r are 0, s, p ', n' and m 'are 1 and R ⁸ is selected from the group consisting of the group consisting of carbon atoms, R ⁹ contains oxygen and R ¹⁰ contains isobenzofuran- (IV) wherein u, i, ii, and iii are a double bond and v is a single bond, the creep conditioner is a benzophenone-3,4,3 ', 4'- Tetracarboxylic acid dianhydride:

wherein q and s are 1000, r and p 'are 0, m' and n 'are 1 and R ⁸ is a trivalent hydrocarbon containing 1 carbon atom, R ¹⁰ is a bivalent hydrocarbon containing 1 carbon atom, t and v Is a single bond and i, ii, and iii are double bonds and A &^lt; ¹ > is a methyl methacrylate monomer, the crepe modifier is a copolymer of 5-vinylisobenzo Furan-l, 3-dione and methyl methacrylate (MMA).

wherein q and s are 1000, r and p 'are 0, m' and n 'are 1 and R ⁸ is a trivalent hydrocarbon containing 1 carbon atom, R ¹⁰ is a bivalent hydrocarbon containing 1 carbon atom, t and v Is a single bond and i, ii, and iii are double bonds and A &^lt; ¹ > is a styrene monomer, the crepe modifier is a copolymer of 5-vinylisobenzofuran- , 3-dione and styrene:

r, q and s are 1000, p 'is 0, m' and n 'are 1 and R ⁸ is a monovalent hydrocarbon containing 1 carbon atom, R ¹⁰ is a bivalent hydrocarbon containing 1 carbon atom and w, t And v is a single bond and i, ii and iii are a double bond, A ¹ is a methyl methacrylate monomer and A ² is a styrene monomer, the creep conditioner is selected from the group consisting of a 5-vinylisobenzofuran-1,3-dione, and styrene, which are polymers of methyl methacrylate,

In another embodiment of the present invention, the polyester composition comprises a crepe modifier of the formula (V)

Wherein R may comprise a heteroatom, or a C ₁ -C ₁₀ hydrocarbyl which may be unsubstituted or substituted with one or more functional moieties;

m ", n ", and o ", independently of one another, may be from 0 to 1,000.

Formula (V) represents the chemical structure of Joncryl®-ADR, available from BASF Corporation, Florham Park, NJ, 07932. The molecular weight of the polymer represented by the formula (V) is less than about 3000.

In certain embodiments of the compounds of formula (V) wherein m ", n", and o "are 100 and R is methyl, the crepe modifier is a copolymer of the formula:

In another embodiment of the present invention, the polyester composition comprises a crepe modifier of the formula (VI)

Wherein R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ , independently of each other, may comprise a heteroatom, S is a carbon atom or a C ₁ -C ₃ divalent or _trivalent hydrocarbon; Each heteroatom, a carbon atom or a C ₁ -C ₃ divalent or _trivalent hydrocarbon, is optionally substituted with one or more C ₁ -C ₁₀ hydrocarbons, which may be unsubstituted or substituted with one or more functional moieties, ≪ / RTI >

i, ii, iii, iv, v, vi, vii, viii, ix, x, and xi are independently of each other a single bond or a double bond; When i is a double bond, ii and vi are single bonds; When ii is a double bond, i, iii, and vii are single bonds; When iii is a double bond, ii, iv, vii, and xi are single bonds; When iv is a double bond, iii, v, and xi are single bonds; When v is a double bond, vi and iv are single bonds; When vi is a double bond, i and v are single bonds; When vii is a double bond, ii, iii, and viii are single bonds; When viii is a double bond, vi and ix are a single bond; When ix is a double bond, viii and x are single bonds; When x is a double bond, ix and xi are single bonds; When xi is a double bond, iv, x, and iii are single bonds.

^{R 11, R 12, R 13} , and R ¹⁴ is refrain containing one carbon atom hydrocarbon is a double bond vi, ii, iv, viii, and x is the i, iii, v, vii, ix is a single bond In certain embodiments of compounds of formula (VI), the crepe modifier is a 1,4,5,8-tetracarboxylic acid-naphthalene dianhydride which is a compound of the formula:

In another embodiment of the present invention, the polyester composition comprises a crepe modifier of formula (VII): < EMI ID =

Wherein R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² independently of one another are a heteroatom, S is a carbon atom or a C ₁ -C ₃ divalent or _trivalent hydrocarbon You can; Each heteroatom, a carbon atom, or a C ₁ -C ₃ divalent or _trivalent hydrocarbon, is optionally substituted with one or more C ₁ -C ₁₀ hydrocarbons, which can be unsubstituted or substituted with one or more functional moieties, Carbamoyl;

xi, xi, xi, xi, xi, xi, xi, xi, xi, vii, vii, viii, xi, xi, xii, xiii, xiv, xv, xvi, Or a single bond; When i is a double bond, ii and vi are single bonds; When ii is a double bond, i, iii, and vii are single bonds; When iii is a double bond, ii, iv, vii, and xi are single bonds; when iv is a double bond, iii, v, xi, and xii are single bonds; When v is a double bond, vi, iv, and xii are single bonds; When vi is a double bond, i and v are single bonds; When vii is a double bond, ii, iii and viii are single bonds; When viii is a double bond, vii and ix are a single bond; When ix is a double bond, viii and x are single bonds; When x is a double bond, ix, xi, and xiii are single bonds; When xi is a double bond, iii, iv, xiii and x are single bonds; When xii is a double bond, v, iv, xvi, and xiv are single bonds; When xiv is a double bond, xii, xvi, xv, and xix are single bonds; When xv is a double bond, xiii, xvii, xiv, and xix are single bonds; When xiii is a double bond, xi, x, xv, and xvii are single bonds; When xvi is a double bond, xii, xiv, and xviii are single bonds; When xviii is a double bond, xvi and xxi are single bonds; When xxi is a double bond, xviii and xxii are single bonds; When xxii is a double bond, xxi, xix, and xxiii are single bonds; When xix is a double bond, xiv, xv, xxii, and xxiii are only a single bond; When xxiii is a double bond, xix, xxii, and xxiv are single bonds; When xxiv is a double bond, xxiii and xx are single bonds; When xx is a double bond, xvii and xxiv are a single bond; When xvii is a double bond, xv, xiii and xx are single bonds.

^{R 15, R 16, R 17} , R 18, R 19, R 20, R 21, and R ²² is and refrain from hydrocarbons which contain from 1 carbon atoms, ii, iv, vi, viii, x, xiv, xvii, xviii (VI) wherein x, y, xxii, and xxiv are double bonds and i, iii, v, vii, xi, xii, xiii, ix, xv, xvi, xix, xxi, xxiii, In an example, the crepe modifier is a perylene-3,4,9,10-tetracarboxylic acid dianhydride of the formula:

The term "heteroatom " as used herein refers to any atom other than carbon or hydrogen. Typically, the heteroatom includes nitrogen, oxygen, or sulfur.

The term " hydrocarbyl "as used herein is used to describe monovalent hydrocarbons that can form a single bond with other atoms within a single chemical compound. The term "bivalent hydrocarbon" as used herein is used to describe hydrocarbons that can form two bonds in a single chemical compound as a double bond to one other atom, or as a separate single bond to two different atoms. As used herein, the term "trivalent hydrocarbon" refers to a monovalent hydrocarbon group that, within a single chemical compound, forms three bonds as a single bond to a single atom, as a double bond and a single bond to two different atoms, It is used to describe hydrocarbons that can be. As used herein, "a sagas carbon atom" refers to a single carbon atom in a single chemical compound, as one triple bond and one single bond at two different atoms, as two double bonds at two different atoms, Is used to describe a carbon atom that can form a double bond and two single bonds or four bonds as four individual single bonds to four different atoms.

The term "hydrocarbon" and "hydrocarbyl" as used herein includes aliphatic, aromatic or aryl groups, cyclic groups, heterocyclic groups, or any combination thereof and halide, alkoxide or amide-substituted derivatives thereof But are not limited to, any substituted derivatives thereof. Also included in the definition of hydrocarbyl are any unsubstituted branched or linear analogs thereof. The hydrocarbyl may be substituted with one or more functional moieties as described below.

Examples of aliphatic groups include but are not limited to alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, alkadienyl groups, cyclic groups, and the like, Branched and linear analogues or derivatives thereof. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, , Nonyl, and decyl. The cycloalkyl moiety may be monocycle or multi-cycle, examples of which include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. Additional examples of alkyl moieties have linear, branched and / or cyclic moieties (e.g., 1-ethyl-4-methyl-cyclohexyl). Representative alkenyl moieties include vinyl, allyl, 1-butenyl, 2-butenyl, isobutylenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1-heptenyl, 2-heptenyl, 3- Decenyl, 3-octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 2-decenyl and 3-decenyl. Representative alkynyl moieties include acetylenyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 3-methyl-1-butynyl, 4-pentynyl, Heptynyl, 2-heptynyl, 6-heptynyl, 1-octynyl, 2-octynyl, 7-octynyl, 1-nonenyl, 8-nonynyl, 1-decynyl, 2-decynyl and 9-decynyl.

Examples of aryl or aromatic moieties include anthracenyl, azulenyl, biphenyl, fluorenyl, indan, indenyl, naphthyl, phenyl, 1,2,3,4-tetrahydro-naphthalene, But are not limited to, substituted derivatives thereof having from 6 to about 10 carbons. Substituted derivatives of aromatic compounds include, but are not limited to, tolyl, xylyl, mesityl, and the like, and any heteroatom-substituted derivatives thereof. In each instance, examples of cyclic groups include, but are not limited to, cycloparaffins, cycloolefins, cycloacetylene, arenes such as phenyl, bicyclic groups, and the like, and substituted derivatives thereof. Accordingly, heteroatom-substituted cyclic and bicyclic groups such as furanyl and isosorbyl are included herein.

(여기서, m은 1 내지 약 10의 정수이며, q는 1 내지 5의 정수임);

(여기서, m은 1 내지 약 10의 정수이며, q는 1 내지 10의 정수임); 및

(여기서, m은 1 내지 약 10의 정수이며, q는 1 내지 9의 정수임)과 같은 기를 포함하지만, 이에 제한되지 않는다. 각 경우에서 및 상기에서 정의된 바와 같이, M은 독립적으로 지방족기; 방향족기; 시클릭기; 및 이들의 임의의 조합; 할라이드-, 알콕사이드- 또는 아미드-치환된 이들의 유도체를 포함하지만, 이에 제한되지 않는 이들의 임의의 치환된 유도체; 1 내지 약 10개의 탄소 원자를 갖는 임의의 기; 또는 수소로부터 선택된다. 일 양태에서, 지방족 및 시클릭 기는

; 이들의 임의의 기하이성질체, 또는 이들의 임의의 치환된 유도체를 포함하지만, 이에 제한되지 않는다.In each case, aliphatic and cyclic groups are groups comprising aliphatic and cyclic moieties, examples of which include,

(Wherein m is an integer from 1 to about 10 and q is an integer from 1 to 5);

(Wherein m is an integer from 1 to about 10 and q is an integer from 1 to 10); And

(Where m is an integer from 1 to about 10 and q is an integer from 1 to 9). In each case and as defined above, M is independently an aliphatic group; An aromatic group; Cyclic group; And any combination thereof; Any substituted derivatives thereof including, but not limited to, halide-, alkoxide- or amide-substituted derivatives thereof; Any group having from 1 to about 10 carbon atoms; Or hydrogen. In one embodiment, the aliphatic and cyclic groups are

; Any of their geometric isomers, or any substituted derivatives thereof.

In each case, the heterocycle comprising one or more heteroatoms is selected from the group consisting of morpholinyl, thiomorpholinyl, thiomorpholinyl S-oxide, thiomorpholinyl S, S-dioxide, piperazinyl, Pyridinyl, pyrrolidinyl, pyrrolinyl, tetrahydropyranyl, piperidinyl, tetrahydrofuranyl, tetrahydrothienyl, homopiperidinyl, homomorpholinyl, homothiomorpholinyl, homothiomorpholinyl S, S-dioxide, oxazolinonyl, dihydropyrazolyl, dihydropyrrolyl, dihydropyridinyl, dihydropyridinyl, dihydropyrimidinyl, dihydrofuryl, dihydropyranyl, tetrahydrothienyl S-oxide , Tetrahydrothienyl S, S-dioxide and homothiomorpholinyl S-oxide, pyridinyl, pyrimidinyl, quinolinyl, benzothienyl, indolyl, indolinyl, pyridazinyl, pyrazinyl, iso Indolyl, isoquinolyl, quinane Wherein R is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, chlorine, bromine, iodine, chlorine, bromine, iodine, Thienyl, pyrrolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, oxazolopyridinyl, imidazopyridinyl, isothiazolyl, naphthyridinyl, cinnolinyl, carbazolyl, Isobenzothiazolyl, isobenzothienyl, isosorbyl, benzoxazolyl, pyrimidinyl, isoxazolyl, isobenzothiazolyl, isothiazolyl, isothiazolyl, isothiazolyl, isothiazolyl, isothiazolyl, Benzothiopyranyl, imidazolidinyl, benzotetrahydrofuranyl, benzotetrahydrothienyl, pyridinyl, benzodioxolyl, triazinyl, phenoxazinyl, phenothiazinyl, phthyridinyl, benzothiazolyl, imidazopyridinyl, imidazo Thiazolyl, dihydrobenzisoxazinyl, Benzothiazinyl, benzoxazinyl, dihydrobenzisothiazinyl, benzopyranyl, benzothiopyranyl, coumarinyl, isomoumarinyl, chromonyl, chromanonyl, pyridinyl-N-oxide, tetrahydroquinoline Dihydroisoquinolinyl, dihydroquinolinyl, dihydroquinolinyl, dihydroquinolinyl, dihydroisoquinolinyl, isoindolinonyl, benzodioxanyl, benzooxazolinonyl, di Pyridazinyl N-oxide, pyrazinyl N-oxide, quinolinyl N-oxide, indolyl N-oxide, indolinyl N-oxide, isoquinolyl N-oxide, pyrimidinyl N-oxide, Oxazole, oxazole, quinazolinyl N-oxide, quinoxalinyl N-oxide, phthalazinyl N-oxide, imidazolyl N-oxide, isoxazolyl N-oxide, Ridinyl N-oxide, indazolyl N-oxide, benzo Oxadiazolyl N-oxide, thiadiazolyl N-oxide, triazolyl N-oxide, tetrazolyl N-oxide, benzothiopyranyl S-oxide, or benzothiopyranyl S, S-dioxide.

The term alkoxy, as used herein, unless otherwise indicated, refers to a moiety of the structure -O-alkyl (wherein alkyl is as defined above).

As used herein, the term acyl refers to a group of C (O) R 'wherein R' is alkyl, aryl, heteroaryl, heterocyclic, alkaryl or aralkyl, or substituted alkyl, aryl, heteroaryl, Heterocyclic, aralkyl or alkaryl, and these groups are as defined above.

Unless otherwise indicated, the term "substituted" refers to a structure or moiety derivative in which the hydrogen atom thereof is replaced by a chemical moiety or functional group, when used to describe a chemical structure or moiety. Non-limiting examples of suitable functional moieties used herein include halide, hydroxyl, amino, amido, alkylamino, arylamino, alkoxy, aryloxy, nitro, acyl, cyano, sulfo, sulfato, mercapto , Imino, sulfonyl, sulfenyl, sulphinyl, sulphamoyl, phosphonyl, phosphinyl, phosphoryl, phosphino, thioester, thioether, anhydride, oxime, hydrazino, carbamyl, , Phosphonates, ethers, ketones, esters, and any other possible functional groups.

III . gas Barrier property  Additive composition

The gas barrier toughening additives provided herein generally include gas barrier additives with reduced volatility as compared to previously found gas barrier additives. As used herein, the terms "gas barrier enhancing additive" and "gas barrier additive" may be used interchangeably as synonyms.

In one embodiment, a gas barrier toughening additive having the formula (I) or (II) is provided:

Wherein X and X ⁶ are independently of each other hydrogen, halide, heteroatom, hydroxyl, amino, amido, alkylamino, arylamino, alkoxy, aryloxy, nitro, acyl, cyano, sulfo, sulfato , Mercapto, imino, sulfonyl, sulfanyl, sulfinyl, sulfamoyl, phosphonyl, phosphinyl, phosphoryl, phosphino, thioester, thioether, anhydride, oxino, hydrazino, carbamyl, , Phosphonato, or a C ₁ -C ₁₀ monovalent hydrocarbon that is unsubstituted or may be substituted with one or more functional moieties;

X ¹ , X ² , X ³ , X ⁴ and X ⁵ independently of one another are heteroatoms or C ₁ -C ₁₀ divalent hydrocarbons wherein each heteroatom or C ₁ -C ₁₀ divalent hydrocarbon is unsubstituted or substituted , One or more functional moieties, or one or more C ₁ -C ₁₀ hydrocarbyl which may be unsubstituted or substituted with one or more functional moieties;

s, t, u, and v are independently of each other a number from 0 to 10.

In certain embodiments, when X ³ comprises a C ₆ or C ₁₀ divalent aromatic hydrocarbon, X and X ⁶ are independently of each other hydrogen, halide, heteroatom, hydroxyl, amino, amido, alkylamino, arylamino Alkoxy, aryloxy, nitro, acyl, cyano, sulfo, sulfato, mercapto, imino, sulfonyl, sulfenyl, sulfinyl, sulfamoyl, phosphonyl, phosphinyl, phosphoryl, A C ₃ -C ₁₀ monovalent cyclic or heterocyclic non-cyclic non-cyclic moiety which may be unsubstituted or substituted with one or more functional moieties, such as, for example, an ester, thioether, anhydride, oxime, hydrazino, carbamyl, phosphonic acid, phosphonato, Aryl hydrocarbons.

In one embodiment of the compound of formula (I) wherein X and X < ⁶ > each comprise a phenyl group, the gas barrier additive comprises a compound having the formula:

In one embodiment of the compound of formula (I) wherein X and X ⁶ each comprise a phenyl group and s and v are 0, the gas barrier additive comprises a compound having the formula:

In one embodiment of the compound of formula (I) wherein X and X ⁶ each comprise a phenyl group and s, t, u, and v are 0, the gas barrier additive comprises a compound having the formula:

In one embodiment of the compound of formula (I) wherein X and X ⁶ each comprise a phenyl group and s, t, u, and v are 0 and X ³ is bissoisorbide, Lt; RTI ID = 0.0 > of dibenzoylisosorbide: < / RTI >

In one embodiment of the compound of formula (I) wherein X and X ⁶ each comprise a phenyl group and s, t, u and v are 0 and X ³ comprises divalent cyclohexane, the gas barrier additive has the formula ≪ / RTI > compounds:

In one embodiment of the compounds of formula (I) wherein X and X ⁶ each comprise a phenyl group and s and v are 0, t and u are 1 and each of X ² and X ⁴ is bivalent C ₁ hydrocarbon, The sex additive comprises a compound having the formula:

(I) wherein X and X ⁶ each comprise a phenyl group and s and v are 0, t and u are 1 and each of X ² and X ⁴ contains a bivalent C ₁ hydrocarbon and X ³ is a divalent hydro- ), The gas barrier additive comprises a compound having the formula: < RTI ID = 0.0 >

(I) wherein X and X ⁶ each comprise a phenyl group and s and v are 0, t and u are 1 and each of X ² and X ⁴ comprises a divalent C ₁ hydrocarbon and X ³ comprises divalent cyclohexane, In an embodiment of the compound, the gas barrier additive comprises a compound having the formula:

In embodiments of compounds of formula (I) wherein X and X < ⁶ > each comprise a naphthyl group, the gas barrier additive comprises a compound having the formula:

In embodiments of the compounds of formula (I) wherein X and X ⁶ each comprise a naphthyl group and s and v are 0, the gas barrier additive comprises a compound having the formula:

In embodiments of the compounds of formula (I) wherein X and X ⁶ each comprise a naphthyl group and s and v are 0 and t and u are 1 and each of X ² and X ⁴ comprises a C ₁ hydrocarbon, The additive comprises a compound having the formula:

X and X ⁶ each comprise a naphthyl group, s and v are 0, t and u are 1 and each of X ² and X ⁴ contains a divalent C ₁ hydrocarbon and X ³ is an ortho-, meta- or para- In embodiments of the compounds of formula (I) wherein the divalent cyclohexane that may be substituted comprises a gas barrier additive, the compound comprises a compound having the formula:

For example, in certain embodiments where the divalent cyclohexane is para-substituted, the gas barrier additive comprises cyclohexane-1,4-diylbis (methylene) di-2-naphthoate, a compound of the formula:

In embodiments of the compounds of formula (II) wherein each of X and X ⁶ comprises a cyclohexyl group, the gas barrier additive comprises a compound having the formula:

In embodiments of the compound of formula (II) wherein X and X ⁶ each comprise a cyclohexyl group and s and v are 0, the gas barrier additive comprises a compound having the formula:

In embodiments of the compounds of formula (II) wherein X and X ⁶ each comprise a cyclohexyl group and s, t, u and v are 0, the gas barrier additive comprises a compound having the formula:

Compounds of formula (II) wherein X and X ⁶ each comprise a cyclohexyl group and the divalent benzene in which s, t, u and v are 0 and X ³ can be ortho-, meta-, or para- The gas barrier additive comprises a compound having the formula: < RTI ID = 0.0 >

For example, in certain embodiments where the divalent benzene is para-substituted, the gas barrier additive comprises dicyclohexyl terephthalate, a compound of the formula:

In another embodiment where the divalent benzene can be meta-substituted, the gas barrier additive comprises dicyclohexyl isophthalate, which is a compound of the formula:

X and X ⁶ each include a cyclohexyl group, and s, t, u, and v is zero and an arbitrary position on the X ³ rings (e.g., 1, 2, 3, 4, 5, 6, 7, or 8), the gas barrier additive comprises a compound of the formula: < RTI ID = 0.0 >

For example, in certain embodiments where the divalent naphthalene is substituted at the 2 and 6 positions, the gas barrier additive comprises dicyclohexyl naphthalene-2,6-dicarboxylate, a compound of the formula:

In embodiments of the compounds of formula (II) wherein X and X < ⁶ > each comprise a benzoate group, the gas barrier additive comprises a compound of the formula:

In embodiments of the compounds of formula (II) wherein X and X ⁶ each comprise a benzoate group and t and u are 0, the gas barrier additive comprises a compound of the formula:

In embodiments of the compounds of formula (II) wherein X and X ⁶ each comprise a benzoate group and t and u are 0, s and v are 1 and X ¹ and X ⁵ each comprise a divalent C ₁ hydrocarbon, The sex additive comprises a compound of the formula:

X and X ⁶ each comprise a benzoate group, t and u are 0, s and v are 1 and X ¹ and X ⁵ each independently represent a divalent C ₁ hydrocarbon and X ³ is an ortho-, meta- or para- In embodiments of the compound of formula (II) wherein the divalent substituent is benzene, the gas barrier additive comprises a compound of the formula:

In certain embodiments in which the divalent benzene is para-substituted, the gas barrier additive comprises bis (2- (benzoyloxy) ethyl) terephthalate, which is a compound of the formula:

In embodiments of formula (II) wherein each of X and X ⁶ comprises a benzoate group, the gas barrier additive comprises a compound of the formula:

In embodiments of formula (II) wherein X and X ⁶ each comprise a benzoate group and s and v are 2 and each of X ¹ and X ⁵ is bivalent C ₁ hydrocarbon, the gas barrier additive comprises a compound of the formula Includes:

X and X ⁶ each comprise a benzoate group, s and v are 2, each of X ¹ and X ⁵ contains a divalent C ₁ hydrocarbon, t and u are 1 and each of X ² and X ⁴ is an ortho-, , Or a para-substituted dibenzoate, the gas barrier additive comprises a compound of the formula: < RTI ID = 0.0 >

X and X ⁶ each comprise a benzoate group, s and v are 2, each of X ¹ and X ⁵ contains a divalent C ₁ hydrocarbon, t and u are 1 and each of X ² and X ⁴ is an ortho-, , Or a para-substituted dibenzoate and X ³ is divalent C ₂ hydrocarbon, the gas barrier additive comprises a compound of the formula:

In certain embodiments where the divalent benzoate is meta-substituted, the gas barrier additive comprises bis (2- (benzoyloxy) ethyl) - ethane-1,2-diyl diisophthalate, which is a compound of the formula:

In embodiments of the compounds of formula (II) wherein X and X ⁶ each comprise an aryloxy group (e.g., phenoxy group), the gas barrier additive comprises a compound of the formula:

In embodiments of the compounds of formula (II) wherein X and X ⁶ each comprise an aryloxy group (e.g., phenoxy group) and t and u are 0, the gas barrier additive comprises a compound of the formula:

Wherein X and X ⁶ each comprise an aryloxy group (e.g., phenoxy) and t and u are 0 and X ³ is ortho-, meta-, or para-substituted, II), the gas barrier additive comprises a compound of the formula:

X and X ⁶ each is an aryloxy group (e.g., phenoxy group), a containing and t and u is 0 and s and v is 1 and X ¹ and X ⁵ is a straight chain divalent comprises a C ₂ hydrocarbon and X ³ is ascended In embodiments of compounds of formula (II) wherein the divalent benzene which may be substituted by lower-, meta-, or para-substituted benzenes, the gas barrier additive comprises a compound of the formula:

For example, in certain embodiments where the divalent benzene is para-substituted, the gas barrier additive comprises bis (2-phenoxyethyl) terephthalate (PEM), which is a compound of the formula:

Other gas barrier enhancing additives suitable for use in the embodiments provided herein are known to those skilled in the art and include but are not limited to those disclosed in U.S. Patent Publication No. 2005/0221036, U.S. Patent Application Publication No. 2006/0275568, and U.S. Patent Application Publication No. 2007/0082156.

IV . Method for preparing polyester composition and container

As noted above, the polyester compositions provided herein are useful for preparing containers for which enhanced gas barrier properties are desired. In summary, such a container is made by molding the above-described polyester composition into a predetermined container by a conventional method such as melt forming. Suitable melt forming processes include, but are not limited to, injection molding, extrusion, thermoforming and extrusion of preforms, which are then blow molded into a bottle. A particularly preferred method for producing the container of the present invention is stretch blow molding.

Methods of introducing gas barrier properties enhancing additives into the container and polyester composition are also provided herein. Such methods are also well known to those skilled in the art. For example, the additive may be supplied directly to the polyester during the injection molding process, pre-blended with the polyester resin prior to injection molding, or introduced at a high concentration with the PET as the masterbatch, followed by injection molding of the preform and stretch blow molding Both can be blended with the polyester resin prior to molding. Those skilled in the art will recognize that these methods can be modified depending on the type of additive used. For example, when using additives in powder form, the polyester resin can be pulverized to reduce the size of the pellets and promote homogeneous blend form.

1 illustrates a system 10 according to one embodiment of the present invention for manufacturing a rigid vessel preform 12 (shown in Fig. 2) and a rigid vessel 14 (shown in Fig. 3) FIG. As shown in FIG. 1, the PET 20 and the gas barrier performance enhancing additive 22 are fed into a feeder or hopper 24 that delivers the components to a hot melt extruder 26 that melts and blends with the polyester . The hot melt extruder 26 then extrudes the molten mixture of the polyester 20 and the gas barrier enhancing additive 22 into the injection molding apparatus 28 to form the preform 12. The preform 12 is cooled and removed from the injection molding apparatus 28 and delivered to an elongate blow molding apparatus 30 that draws the preform 12 to the final rigid vessel 14 by blow blow molding.

In the preform production, the melt residence time is preferably less than 5 minutes, and more preferably from about 1 to about 3 minutes. The melting temperature is preferably about 260 to about 300 캜, more preferably about 270 to about 290 캜. The melt residence time begins when the PET 20 and the gas barrier enhancing additive 22 begin to melt and enter the melt extruder 26 and the molten blend is injected into an injection mold for forming the preform 12 And is terminated.

V. Container

As is well known to those skilled in the art, the container can be made by blow molding the container preform. Examples of suitable preforms and container structures are described in U.S. Patent No. 5,888,598, which is incorporated herein by reference in its entirety to preforms and container structures.

The polyester container preform 12 is shown in Fig. The preform 12 includes a threaded neck finish 112 that is manufactured by injection molding or compression molding a PET-based resin and terminates at the lower end of the capping flange 114. Beneath the capping flange 114 is a generally cylindrical section 116 that terminates in a section 118 of outer diameter that gradually increases to provide an increased wall thickness. Below this section 118, there is a long body section 120.

The preform 12 shown in Fig. 2 may be stretch blow molded to form the container 14 shown in Figs. The container 14 includes a shell 124 that includes a thread neck finish 126 defining an inlet 128, a capping flange 130 below the thread neck finish, a pointed section 132 extending from the capping flange, A body section 134 extending to the bottom of the container, and a base 136 of the bottom of the container. The container 14 is suitably used to produce the packaged beverage 138, as shown in FIG. The wrapped beverage 138 includes a beverage, such as a soda carbonate drink disposed in the container 14, and a stop 140 to seal the inlet 128 of the container.

The polyester container may optionally comprise a plurality of layers. Those skilled in the art will recognize that the polyester composition comprising the polyester and the gas barrier additive may be disposed in any one of the one or more layers of such a multilayer container. For example, a polyester composition comprising a polyester and a gas barrier toughening additive may be disposed between two or more outer layers.

The preform 12, the container 14 and the packaged beverage 138 are examples of applications using the preform of the present invention. It will be appreciated that the processes and equipment provided herein may be used to produce preforms and containers having various configurations.

The present invention is further illustrated by the following examples, but is not construed to limit the scope of the invention in any way. On the contrary, it is to be clearly understood that various embodiments, modifications and equivalents may be resorted to, after reading the detailed description of the invention, to those skilled in the art without departing from the spirit of the invention and / or appended claims.

Example

Example  One: Preform and Stretching Blow Molded  Vessel

The polyester composition was prepared by blending 1105 polyester resin (Invista, Spartanburg, SC) with grinding and pyromellitic dianhydride (PMDA) and JONCRYL (R), 500 to 2500 ppm crepe control agents.

The polyester composition was injection-molded using a conventional method to obtain a container preform. The vessel preforms exhibited good quality in terms of transparency and appearance, without any indication of buildup on the core pin or in other parts of the thread split and injection molding apparatus, Suggesting that there was no substantial plate-out of the mold surface. Thereafter, the preliminarily molded container was subjected to stretch blow molding using a conventional method to obtain transparent, colorless, and indistinguishable bottles with the naked eye.

Example 2: Shelf life and barrier improvement factor of a PET container containing a crepe control agent [

A container was prepared as described in Example 1 using both the polyester described above, both alone and with 500 to 2500 ppm crepe modifier. Creep modifiers included PMDA and JONCRYL®.

The vessel was filled with dry ice to an internal pressure of 56 psi. The percent disappearance of carbon dioxide from the bottle was measured at 22 占 폚 and 50% RH using the method described in U.S. Patent No. 5,473,161, all of which are hereby incorporated by reference. The barrier improvement factor (BlF) is defined as the ratio of the loss of carbon dioxide in the polyester container containing no additives divided by the loss of carbon dioxide in the polyester container containing the additives. In addition, the shelf life of simulated carbonated soft drinks for each container was calculated as described in U.S. Patent No. 5,473,161. The results are summarized in the following table.

Table 1: Summary of container storage life and BIF

Example  3: creep modifier and gas Barrier property  Containing additives PET  The shelf life of the container and Barrier property  Improvement factor

Both of the above-described polyesters were used alone, and in combination with various crepe modifiers and gas barrier additives to prepare containers. The shelf life and barrier properties of the container were measured as described in Example 2. < tb > < TABLE >

Table 2: Container Shelf Life, and BIF Summary

Example  4: Creep modifier and gas Barrier property  Containing additives PET  The average bottle of the container Creep rate (%)

Both of the above-described polyesters were used alone, and in combination with various crepe modifiers and gas barrier additives to prepare containers. The average bottle creep percentage (%) is shown in Table 3 and is shown in FIG. Creep measurements were performed by measuring the volume displacement of the water by the bottle at a given temperature.

Table 3: Summary of 8 week container creep

As can be seen from the above, the addition of the crepe modifier reduced the creep of the container as compared to the control container made from the additive-free polyester composition.

Example  5: Creep modifier and gas Barrier property  Containing additives PET  The aesthetic qualities of containers color  & Turbidity ( haze ))

Both of the above-described polyesters were used alone, and in combination with various crepe modifiers and gas barrier additives to prepare containers. The color of the container was measured with a Hunter lab colorimeter. These results are shown in Table 4 below. The Hunter L ^* , a ^* , b ^* color space is a three-dimensional rectangular color space based on opponent-colors theory, extending to the yellow region where White on the L ^* And black is 0, red on the a ^* (red-green) axis is positive, green is negative, and the middle is 0; On the b ^* (blue-yellow) axis, the yellow is positive, the blue is negative, and the middle is zero. DE ^* is a measure of the overall color difference, which is calculated by taking the square root of the sum of the squares of the changes in L ^* , a ^* , b ^* . The data in Table 4 below is the average for 9 measurements.

Table 4: Turbidity analysis of vessels

As can be seen from the above, the use of controlled amounts of gas barrier additives generally did not significantly impair the aesthetic appearance of the container. In particular, it should be noted that the amount of crepe modifier has been shown to directly affect the turbidity of the container compared to a container made from polyester without additives.

It will be appreciated that the above examples are merely preferred embodiments of the present disclosure and that numerous changes and modifications can be made herein without departing from the spirit and scope of the invention as defined by the following claims and their equivalents.

Example  6

The containers were also made using other polyester resins with gas barrier toughening additives and / or creep control agents. Other polyester resins included 1103A (Invista, Spartanburg, South Carolina) and MMP 804 (PET Processors L.L.C., Painesville, Ohio).

The CO ₂ penetration test was used to determine the shelf life of the container. The bottle was filled with carbonated water at 4.2 v / v, and the loss of carbon dioxide from the bottle was measured using QuantiPerm at 22 < 0 > C and 50% RH. Penetration rate (mL / pkg / day) was used to calculate the loss rate and shelf life of carbonation per week. The absorption rate was estimated by QuantiPerm software, and the volume expansion rate was measured for each container.

Table 5: Summary of container storage life

As can be seen from the above, the addition of gas barrier additives and crepe modifier significantly increased the shelf life of containers made from different types of polyester resins.

Example  7: PEM ≪ / RTI > and Stretching Blow Molded  Manufacture of containers

A polyester composition was prepared by blending a pulverized 1103A polyester resin (Invista, Spartanburg, SC) with 3 or 4 weight percent PEM, a gas barrier additive having the following formula:

The polyester composition was injection-molded using a conventional method to obtain a container preform. The vessel preform exhibits good quality in terms of transparency and appearance, without any indication of accumulation on the core pin or in other parts of the thread split and injection molding apparatus, and there is no substantial mold surface separation on the injection molding apparatus Respectively. Thereafter, the vessel preform was subjected to stretch blow molding using a conventional method to obtain a bottle which was transparent, colorless, and indistinguishable from the naked eye.

The amount of additives and the intrinsic viscosity (I.V.) of the polyester composition, preform and container are described in the following table.

Table 6: Polyester compositions and preforms I.V.

As illustrated above, an acceptable I.V., 0.03 dL / g loss was achieved during the conversion of the resin to the preform. No significant difference was observed between the 1103A control preform and the preform molded with 3% and 4% PEM-1. The I.V. of the preforms produced with 750 ppm of PMDA and 4% of PEM-1 was significantly higher than that formed without PMDA.

It will be appreciated by those skilled in the art that the observation of a decrease in I.V. as the amount of gas barrier additive increases is not uncommon and I.V. can be increased by using a polyester resin having a higher I.V.

Example  8

A container was prepared using the conventional method using the polyester composition of Example 7 and evaluated using the method described above. The results are summarized in the following table.

Table 7: Shelf life and barrier improvement factor (BIF) results

As illustrated above, the addition of a gas barrier additive to the polyester significantly enhanced the shelf life and gas barrier properties of the container compared to a container made from polyester without a gas barrier additive. Surprisingly, the addition of only 3% by weight of PEM-1 increased the container BIF by almost 20% (1.18) and increased the shelf life approximately two weeks.

Example  9

JONCRYL® ADR-4368-C may be used in the containers described herein, but problems can occur during processing. While not wishing to be bound by any particular theory, it is believed that the lower melting point of the JONCRYL (R) material causes the JONCRYL (R) material to soften in the feed throat of the injector, causing the PET material to aggregate. Thus, CESA EXTEND (Clariant Corporation, Delaware, United States) may be used instead. CESA EXTEND ™ is designed to eliminate cohesion problems during injection molding by incorporating the JONCRYL® material into a low melting point carrier. In this example, a container made with CESA EXTEND (TM) was tested.

Other containers in this example contained PMDA incorporated into LNO (TM) (Phoenix Technologies International LLC, Bowling Green, Ohio) pellets. These materials are designed to test the possibility of incorporation of PMDA into recycled materials after consumption. The combination of these materials offers the possibility of eliminating the need for a separate feed in a manufacturing environment. PMDA was blended with two loading levels, ESPS ("Extremely Small Particle Size") (Phoenix Technologies International LLC, Bowling Green, Ohio), a fine particulate PET powder regenerated at 2500 ppm and 10000 ppm. These blends were then compressed with LNO (TM) c pellets. The pellet quality was tested using a pellet durability test. The higher the result, the higher the durability of the pellet. There are up to 100 pellet durability indexes. The results were 96.6 and 96 for loading levels of 2500 ppm and 10000 ppm, respectively. Typical results for LNO (TM) c pellets were 98 or higher, and the lower limit used for quality control was 96.0.

The additives described above were incorporated into a preform made from 1103 A PET resin (Invista). The preform and the formed container were prepared by the conventional method described herein. Thereafter, the FTIR test was performed to determine the shelf life of the container using the method described in U.S. Patent No. 5,473,161. This test was performed with a Perkin-Elmer® FT IR spectrometer with supported hardware fixtures and software by the Coca-Cola Company. The following table contains the FTIR results. This data compares containers prepared with 1103A without the additives labeled "1103 A control ". Based on the preliminary data, the difference between the expected shelf life for the variable is small. It was predicted that the container made with 1103 A / 10,000 ppm LNO (c) (final 750 ppm) would be the biggest improvement. The final FTIR predicted a longer shelf life than the initial data, but the shelf life improvement factors remained unchanged.

Table 8: Preliminary and Final FTIR Results

Claims (22)

A crepe control agent comprising a polyester, a compound of formula (I), and a gas barrier enhancing additive comprising a compound of formula (A) or (B) Wherein the creep control agent is present in the polyester composition in an amount of from 200 to 2000 ppm,

In the above formula (I), R ¹ , R ² , R ³ and R ⁴ may independently of each other be a hetero atom, S may be a carbon atom, or a C ₁ -C ₃ divalent or _trivalent hydrocarbon; Each heteroatom, or a carbon atom, or a C ₁ -C ₃ divalent or _trivalent hydrocarbon, may be unsubstituted or substituted with one or more C ₁ -C ₁₀ alkyl groups, which may be unsubstituted or substituted with one or more functional moieties, Hydrocarbyl,
i, ii, iii, iv, v and vi independently of one another include a single, double or triple bond; When i is a double bond, ii and vi are single bonds; When ii is a double bond, i and iii are single bonds; When iii is a double bond, ii and iv are single bonds; When iv is a double bond, iii and v are single bonds; When v is a double bond, iv and vi are single bonds; When vi is a double bond, i and v are single bonds; vii may not be a single bond, a double bond, or R ³ and R ⁴ at all;
m, n, o, and p independently of one another can be 0 or 1; when m is 0, bonds ii and iii form a single continuous bond; when n is 0, the bonds vi and v form a single continuous bond; when o is 0, R < ⁴ > is bonded to R < ¹ > when p is 0, R < ³ > is bonded to R < ² > by a single bond;
In the above formula (A) or (B), X and X ^6, independently of each other, hydrogen, halide, a cycloalkyl, hydroxyl, amino, amido, alkylamino, arylamino, alkoxy, aryloxy, nitro, acyl, A thioether, an anhydride, a thioether, a thioether, a thioether, a thioether, a thioether, a thioether, a thioether, a thioether, a cyano, a sulfo, a sulfato, a mercapto, an imino, a sulfonyl, a sulfenyl, a sulfinyl, Oxino, hydrazino, carbamyl, phosphonic acid, phosphonato, or a C ₁ -C ₁₀ monovalent hydrocarbon which is unsubstituted or may be substituted with one or more functional moieties;
X ¹ , X ² , X ³ , X ⁴ and X ⁵ independently of one another are heteroatoms or C ₁ -C ₁₀ divalent hydrocarbons wherein each heteroatom or C ₁ -C ₁₀ divalent hydrocarbon is unsubstituted or substituted , One or more functional moieties, or one or more C ₁ -C ₁₀ hydrocarbyl which may be unsubstituted or substituted with one or more functional moieties;
s, t, u, and v are independently of each other a number from 0 to 10;
When X ³ comprises a C ₆ or C ₁₀ divalent aromatic hydrocarbon, X and X ⁶ are, independently of each other, hydrogen, halide, heteroatom, hydroxyl, amino, amido, alkylamino, arylamino, alkoxy, aryloxy , Nitro, acyl, cyano, sulfo, sulfato, mercapto, imino, sulfonyl, sulfolenyl, sulfinyl, sulfamoyl, phosphonyl, phosphinyl, phosphoryl, phosphino, thioester, thioether, An anhydride, an oxime, a hydrazino, a carbamyl, a phosphonic acid, a phosphonate, or a C ₃ -C ₁₀ monocyclic or heterocyclic non-aryl hydrocarbon which is unsubstituted or may be substituted with one or more functional moieties . The container of claim 1, wherein the polyester comprises polyethylene terephthalate. 3. The poly (ethylene terephthalate) composition of claim 2, wherein the polyester comprises less than 20% diacids, less than 10% glycol, or both, based on 100 mole% Containing copolymer. A packaged beverage comprising a beverage introduced into the container of claim 1 and a seal for sealing the beverage in the package. 2. The creep conditioner of claim 1, wherein m and n are 1; o and p are 0; R < ¹ > and R < ² > are monovalent hydrocarbons containing one carbon atom; i, iii, and v are double bonds; wherein the creep conditioner is a compound of formula (I), wherein ii, iv, and vi are single bonds, wherein the creep conditioner is a compound of the formula:

. A polyester composition comprising a polyester, a crepe modifier comprising a compound of formula (II), and a gas barrier enhancing additive comprising a compound of formula (A) or formula (B) Wherein the creep control agent is present in the polyester composition in an amount of from 200 to 2000 ppm,

In the formula (II), A, A ', A ", E, D, G, G', G", L, and J are independently selected from heteroatoms, Inc. carbon atoms, or a divalent C ₁ -C ₃ or together May contain tridentate hydrocarbons; Each heteroatom, a carbon atom or a C ₁ -C ₃ divalent or _trivalent hydrocarbon, is optionally substituted with one or more C ₁ -C ₁₀ hydrocarbons, which may be unsubstituted or substituted with one or more functional moieties, Carbamoyl;
i, ii, iii, iv, v, vi, vii, viii, ix, and x may independently of each other include a single or double bond; When i is a double bond, ii and v are single bonds; When ii is a double bond, i and iii are single bonds; When iii is a double bond, ii and iv are single bonds; When iv is a double bond, iii and v are single bonds; When v is a double bond, i and iv are single bonds; When vi is a double bond, vii and x are single bonds; When vii is a double bond, vi and viii are single bonds; When viii is a double bond, vii and ix are single bonds; When ix is a double bond, viii and x are single bonds; When x is a double bond, vi and ix are single bonds;
b and g are 1 and c, d, e, f, h, i, j and k are independently of each other 0 or 1;
a may be 0 or 1;
R ⁵ is C _1, which may be unsubstituted or substituted with, at least one functional part, of one or more C ₁ -C ₁₀ hydrocarbyl with at least one heteroatom, or it is unsubstituted or may be substituted with at least one functional part - C ₁₀ divalent hydrocarbon or heteroatom;
In the above formula (A) or (B), X and X ^6, independently of each other, hydrogen, halide, a cycloalkyl, hydroxyl, amino, amido, alkylamino, arylamino, alkoxy, aryloxy, nitro, acyl, Wherein the substituent is selected from the group consisting of halogen, cyano, sulfo, sulfato, mercapto, imino, sulfonyl, sulfolenyl, sulfinyl, sulfamoyl, phosphonyl, phosphinyl, phosphoryl, phosphino, thioester, thioether, Hydrazino, carbamyl, phosphonic acid, phosphonato, or a C ₁ -C ₁₀ monovalent hydrocarbon which is unsubstituted or may be substituted with one or more functional moieties;
X ¹ , X ² , X ³ , X ⁴ and X ⁵ independently of one another are heteroatoms or C ₁ -C ₁₀ divalent hydrocarbons wherein each heteroatom or C ₁ -C ₁₀ divalent hydrocarbon is unsubstituted or substituted , One or more functional moieties, or one or more C ₁ -C ₁₀ hydrocarbyl which may be unsubstituted or substituted with one or more functional moieties;
s, t, u, and v are independently of each other a number from 0 to 10;
When X ³ comprises a C ₆ or C ₁₀ divalent aromatic hydrocarbon, X and X ⁶ are, independently of each other, hydrogen, halide, heteroatom, hydroxyl, amino, amido, alkylamino, arylamino, alkoxy, aryloxy , Nitro, acyl, cyano, sulfo, sulfato, mercapto, imino, sulfonyl, sulfolenyl, sulfinyl, sulfamoyl, phosphonyl, phosphinyl, phosphoryl, phosphino, thioester, thioether, An anhydride, an oxime, a hydrazino, a carbamyl, a phosphonic acid, a phosphonate, or a C ₃ -C ₁₀ monocyclic or heterocyclic non-aryl hydrocarbon which is unsubstituted or may be substituted with one or more functional moieties . A polyester composition comprising a polyester, a crepe modifier comprising a compound of formula (III), and a gas barrier toughening additive comprising a compound of formula (A) or (B) Wherein the creep control agent is present in the polyester composition in an amount of from 200 to 2000 ppm,

In the formula (III), R ⁶ and R ⁷ are, independently of each other, unsubstituted or substituted with one or more functional moieties, one or more heteroatoms, or one or more C ₁ - C ₁ -C ₅ divalent hydrocarbon which may be substituted with C ₁₀ hydrocarbyl;
In the above formula (A) or (B), X and X ^6, independently of each other, hydrogen, halide, a cycloalkyl, hydroxyl, amino, amido, alkylamino, arylamino, alkoxy, aryloxy, nitro, acyl, Wherein the substituent is selected from the group consisting of halogen, cyano, sulfo, sulfato, mercapto, imino, sulfonyl, sulfolenyl, sulfinyl, sulfamoyl, phosphonyl, phosphinyl, phosphoryl, phosphino, thioester, thioether, Hydrazino, carbamyl, phosphonic acid, phosphonato, or a C ₁ -C ₁₀ monovalent hydrocarbon which is unsubstituted or may be substituted with one or more functional moieties;
X ¹ , X ² , X ³ , X ⁴ and X ⁵ independently of one another are heteroatoms or C ₁ -C ₁₀ divalent hydrocarbons wherein each heteroatom or C ₁ -C ₁₀ divalent hydrocarbon is unsubstituted or substituted , One or more functional moieties, or one or more C ₁ -C ₁₀ hydrocarbyl which may be unsubstituted or substituted with one or more functional moieties;
s, t, u, and v are independently of each other a number from 0 to 10;
When X ³ comprises a C ₆ or C ₁₀ divalent aromatic hydrocarbon, X and X ⁶ are, independently of each other, hydrogen, halide, heteroatom, hydroxyl, amino, amido, alkylamino, arylamino, alkoxy, aryloxy , Nitro, acyl, cyano, sulfo, sulfato, mercapto, imino, sulfonyl, sulfolenyl, sulfinyl, sulfamoyl, phosphonyl, phosphinyl, phosphoryl, phosphino, thioester, thioether, An anhydride, an oxime, a hydrazino, a carbamyl, a phosphonic acid, a phosphonate, or a C ₃ -C ₁₀ monocyclic or heterocyclic non-aryl hydrocarbon which is unsubstituted or may be substituted with one or more functional moieties . A polyester composition comprising a polyester, a crepe modifier comprising a compound of formula (V), and a gas barrier enhancing additive comprising a compound of formula (A) or (B) Wherein the creep control agent is present in the polyester composition in an amount of from 200 to 2000 ppm,

In the above formula (V), R may include a C ₁ -C ₁₀ hydrocarbyl or heteroatom which may be unsubstituted or substituted with one or more functional moieties;
m ", n ", and o ", independently of each other, can be from 0 to 1,000, and at least one of m ", n ", and o "
In the above formula (A) or (B), X and X ^6, independently of each other, hydrogen, halide, a cycloalkyl, hydroxyl, amino, amido, alkylamino, arylamino, alkoxy, aryloxy, nitro, acyl, Wherein the substituent is selected from the group consisting of halogen, cyano, sulfo, sulfato, mercapto, imino, sulfonyl, sulfolenyl, sulfinyl, sulfamoyl, phosphonyl, phosphinyl, phosphoryl, phosphino, thioester, thioether, Hydrazino, carbamyl, phosphonic acid, phosphonato, or a C ₁ -C ₁₀ monovalent hydrocarbon which is unsubstituted or may be substituted with one or more functional moieties;
X ¹ , X ² , X ³ , X ⁴ and X ⁵ independently of one another are heteroatoms or C ₁ -C ₁₀ divalent hydrocarbons wherein each heteroatom or C ₁ -C ₁₀ divalent hydrocarbon is unsubstituted or substituted , One or more functional moieties, or one or more C ₁ -C ₁₀ hydrocarbyl which may be unsubstituted or substituted with one or more functional moieties;
s, t, u, and v are independently of each other a number from 0 to 10;
When X ³ comprises a C ₆ or C ₁₀ divalent aromatic hydrocarbon, X and X ⁶ are, independently of each other, hydrogen, halide, heteroatom, hydroxyl, amino, amido, alkylamino, arylamino, alkoxy, aryloxy , Nitro, acyl, cyano, sulfo, sulfato, mercapto, imino, sulfonyl, sulfolenyl, sulfinyl, sulfamoyl, phosphonyl, phosphinyl, phosphoryl, phosphino, thioester, thioether, An anhydride, an oxime, a hydrazino, a carbamyl, a phosphonic acid, a phosphonate, or a C ₃ -C ₁₀ monocyclic or heterocyclic non-aryl hydrocarbon which is unsubstituted or may be substituted with one or more functional moieties . 9. A container according to claim 8 wherein the creep conditioner comprises a compound of formula (V) wherein m ", n", and o "are 100 and R is methyl,

. Of claim 1 and claim 6 to 8 according to any one of claims, wherein the gas barrier strengthening additives, X and X ⁶ respectively and include a phenyl group, and s, t, u, and v is 0 X ³ is divalent (I) comprising isosorbide, wherein the gas barrier enhancing additive comprises a compound of the formula: < EMI ID =

. According to claim 1 and claim 6 to 8 as set forth in wherein the gas barrier sex enhancement additive, and each of which includes a group X, and X ⁶ and s and v is 0 and t and u are 1, X ^2, and X < ⁴ > each comprise a compound of formula (I) wherein the bivalent C ₁ hydrocarbon and X ³ comprises bivalent cyclohexane, wherein the gas barrier enhancing additive comprises a compound of the formula:

. Of claim 1 and claim 6 according to any one of claim 8, wherein assuming that the gas barrier enhancement additive, X and X ⁶ each include a naphthyl group, and s and v is 0 and t and u 1 X ² And X < ⁴ > each include a compound of formula (I) wherein the bivalent C ₁ hydrocarbon and X ³ comprises bivalent cyclohexane, wherein the gas barrier enhancing additive comprises a compound of the formula:

. The gas barrier property enhancing additive according to any one of claims 1 and 6 to 8, wherein each of X and X ⁶ contains a cyclohexyl group and s, t, u and v are 0 and X ³ is (II) comprising a divalent benzene, wherein the gas barrier enhancing additive comprises a compound of the formula:

. The gas barrier property enhancing additive according to any one of claims 1 to 6, wherein each of X and X ⁶ contains a cyclohexyl group and s, t, u, and v are 0 and X ³ (II) wherein the gas barrier enhancing additive comprises a compound of the formula: < EMI ID =

. A gas barrier property enhancing additive according to any one of claims 1 to 6, wherein X and X ⁶ each comprise a benzoate group, t and u are 0, s and v are 1 and X ¹ and X ⁵ containers each of which contains a compound of the divalent hydrocarbon group include C ₁ and including a compound of formula (II) X ³ is a divalent benzene, to an enhanced gas barrier additive formula:

. The method according to any one of claim 1 and claims 6 to 8, the gas barrier strengthening additives, X and X ⁶ each comprising a benzoate and s and v is 2 and X ¹ and X ⁵ each tooth Comprising a compound of formula (II) comprising a C ₁ hydrocarbon and wherein t and u are 1 and each of X ² and X ⁴ comprises a divalent benzoate and X ³ comprises a divalent C ₂ hydrocarbon, A container comprising a compound of the formula:

.

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